CN107586367A - The method that sustained-release polycarboxylic water reducer is prepared based on ATRP - Google Patents
The method that sustained-release polycarboxylic water reducer is prepared based on ATRP Download PDFInfo
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Abstract
The present invention relates to a kind of method that sustained-release polycarboxylic water reducer is prepared based on ATRP.The present invention first carries out ATRP to unsaturated acyl amine minor comonomer using halogenated compound initiator and prepares polymeric monomer initiator, triggers esters of unsaturated carboxylic acids to carry out ATRP with salt unsaturated carboxylic acid minor comonomer and unsaturated polyether polymeric monomer by polymeric monomer initiator in the presence of catalyst with part and is made.Present invention process is reasonable, simple to operate, preparation cost is low, environment friendly and pollution-free, and the sustained-release polycarboxylic water reducer prepared using this invention has slow release effect to the mobility of concrete, the loss of the concrete slump caused by long-time is transported can be effectively prevented.Polycarboxylate water-reducer prepared by this method also has controllable molecular weight, narrow molecular weight distribution, the programmable advantage of molecular structure, has larger application potential.
Description
Technical field
The present invention relates to a kind of technical field of cement concrete sustained-release polycarboxylic water reducer, one kind is related specifically to
Prepare polymeric monomer initiator using unsaturated acyl amine minor comonomer triggers unsaturated polyether polymeric monomer and unsaturated carboxylic acid class small again
Monomer carries out the specific preparation method that ATRP prepares sustained-release polycarboxylic water reducer.
Background technology
In recent years, as China's building trade is quickly grown, concrete works application problem is increasingly notable, as concrete is former
Material is by regional impact difference is big, slump-loss is big, Concrete At High Temperature moisture evaporation is too fast in coagulation degree transportation etc.
Problem, more higher requirements are proposed to water reducer.The water reducer that application prospect is best, combination property is optimal in the world at present
It is poly carboxylic acid series water reducer, water-reducing rate is far above naphthalene water reducer, and has simple, the product asepsis environment-protecting of working condition etc. excellent
Point.But in engineer applied, still exist when raw material quality or transport/construction caused by various extraneous factors
The problem of concrete flowability loss is too fast, the method for enjoying favor at present is to realize concrete by the modification of chemical admixture
The holding of mobility, using sustained-release polycarboxylic water reducer its dispersion effect can be made slowly to release during concrete mixes and stirs
Release, so as to extend the holding capacity of concrete flowability.
Sustained-release polycarboxylic water reducer has a variety of synthetic methods at present, and the technique of wherein monomer direct polymerization method is relatively simple
It is single but very poor to the control effect of molecular weight；Polymerization Post functionalization method can prepare the polycarboxylic acids of difference in functionality, but its synthesis by
Polymeric monomer product category limits, it is difficult to adjusts the composition and molecular weight of polycarboxylic acids, practical operation is more difficult；In-situ polymerization is with connecing
The production cost of branch polymerization is low, but polymeric monomer grafting is uncontrollable, is unfavorable for designing molecular structure.Different from these tradition freely
Base polymerize, and ATRP is that there is the one kind proposed first by doctor Wang Jinshan narrow molecular weight distribution, molecule to set
The radical living polymerization for the features such as meter ability is strong, use range is wide, its mechanism of action polymerize different from conventional free radical.Pass
Due to easily there is chain tra nsfer and chain termination reaction in system radical polymerization, it is desirable that extremely low number of free radical can be realized
Reaction speed is reduced, so as to suppress the generation of side reaction；ATRP just so, free radical activity kind with
Dormancy inter-species establishes a Fast-Balance reaction, and a free radical is specifically had while Raolical polymerizable
The reversible transfer balanced reaction of spike and organic macromolecule halide dormancy kind so that free radical activity kind remain at compared with
Low concentration, it is similar to so as to avoid in conventional free radical polymerization because the chain tra nsfer and chain that number of free radical is too high and occurs are whole
Only react and then cause molecular weight uncontrollable and be distributed the problems such as wide.The reversible reaction of the radical polymerization includes halogen atom from having
Machine halide arrives the atom transfer process of one iterative cycles of macromolecular halide, therefore referred to as atom to metal halide again
Transferring free-radical polymerization.In view of the remarkable advantage of the polymerization, its market potential is huge, the agent of application dispersed throughout, table
The pluronic polymers such as face activating agent, adhesive, solubilizer and green chemical, electronic information material and biological medicine material are led
Domain.
Patent CN103482897 (publication date：On March 19th, 2014) report a kind of sustained-release polycarboxylic high-performance diminishing
The preparation method of agent.The invention be by unsaturated APEO and the unsaturated minor comonomer containing carboxyl and ester bond in initiator and
Copolyreaction is carried out in the presence of chain-transferring agent, pH value is adjusted to neutrality afterwards, that is, obtains sustained-release polycarboxylic water reducer.Should
By the ester group in monomer, gradually hydrolysis is discharged to increase carboxyl quantity under alkaline environment for invention, makes the water reducer in body of cement
Scattered efficiency can be kept in system in a long time, reaches the purpose for maintaining the slump.But synthesis mechanism used in the invention
Conventional free radical is still fallen within technique to polymerize, and is existed it is difficult to control the molecular weight of polymerizate, molecular weight distribution, functional group's distribution
And the problems such as microcosmic segment sequence arrangement.
Patent CN101550204 (publication date：On October 7th, 2009) report it is a kind of using polyethylene glycol as polymerisation medium,
The method that high-molecular compound is prepared by ATRP.The invention is sequentially added in the presence of ultrasonic wave
Polyethylene glycol, catalyst, part and unsaturated monomer, initiator is added after logical nitrogen deoxygenation and carries out polymerisation, reaction knot
Shu Houyong methanol purifications obtain linear polymer.The process operation is simple, cost is cheap, green, is adapted to industry
Metaplasia production is promoted.However, the invention uses polyethylene glycols monomer to carry out ATRP, point of product
Not containing this kind of functional group that can provide electrostatic repulsion of carboxyl in minor structure, and nonideal pectination polycarboxylate water-reducer structure,
It is difficult to similar water reducer and adsorbs the effect on cement granules, therefore is difficult to apply to cement water reducing agent field.
Patent CN105968266 (publication date：On September 28th, 2016) report a kind of superpower decentralized polycarboxylic acids and efficiently subtract
The preparation method of aqua.The invention be first by unsaturated Amino End Group minor comonomer and unsaturated esters minor comonomer chain-transferring agent work
Redox radical polymerization is carried out under and prepares Amino End Group copolymer, then by Amino End Group copolymer and halogen acyl halide organic molecule
Carry out esterification to obtain holding halogen base co-polymer, finally by end halogen base co-polymer and unsaturated esters minor comonomer in transition gold
Category compound reacts to obtain high-efficiency water-reducing agent of poly-carboxylic acid with carrying out atom transfer radical copolymerization in the presence of part.This method can
The molecular weight and molecular structure of water reducer are controlled, reaction efficiency is high, nontoxic pollution-free, and properties of product are stable.But the invention exists
The method that conventional free radical polymerization is employed during backbone polymerization, the synthesis of backbone molecule is difficult to control, and due to substep
Block polymerization causes carboxylic group skewness on molecular backbone, so as to have impact on polycarboxylate water-reducer molecule in cement granules
The absorption stability on surface.
In the presently disclosed field patent, polycarboxylate water-reducer has in addition to good workability and mobility
Also there is a certain degree of slow release effect a bit, but still all there is some shortcomings.It is that synthetic method is traditional mostly first
Radical polymerization, this just occurs, and polycarboxylic acids molecular weight is uncontrollable, molecular weight distribution is wider, Molecular Design degree of realization is low
Problem, inventor reaches preferable performance often through reaction raw materials and its proportioning is changed, but few people attempt new gather
Conjunction method；Although as it was noted above, report of the existing part on ATRP, its polymerizate is simultaneously uncomfortable
For polycarboxylate water-reducer field, product molecule structure is not containing anchoring groups such as carboxyls, it is difficult to realizes that similar water reducer absorption exists
The effect of cement particle surface, enough electrostatic repulsions can not be provided；Also some patent application ATRP systems
Standby polycarboxylate water-reducer, but its backbone polymerization still falls within conventional free radical polymerization, and molecular weight is difficult to control, and its block structure also can
Cause the application performance of polycarboxylate water-reducer bad.Therefore, using ATRP prepare molecular weight it is controllable, point
The regular preferable polycarboxylic acid polymer of son amount narrowly distributing, molecular structure, applied to sustained-release polycarboxylic water reducer field, is advantageous to
More excellent mobility and fluidity retention property are realized, while also ensures that its technique is simple, preparation cost is cheap, is easy to work
Industry metaplasia is produced, and relevant this respect work has no report both at home and abroad.
The content of the invention
It is an object of the present invention to provide a kind of side that sustained-release polycarboxylic water reducer is prepared based on ATRP
Method.The present invention carries out ATRP to unsaturated acyl amine minor comonomer using halogenated compound initiator and formed greatly
Monomer initiator, afterwards by polymeric monomer initiator initiation unsaturated ether polymeric monomer and unsaturated carboxylate type minor comonomer and not
Saturated carboxylic acid salt carries out ATRP and is made.The present invention is first according to atom transition free radical polymerization reaction principle
Macromole evocating agent is prepared for, triggers unsaturated ether polymeric monomer to polymerize with carboxylic acids minor comonomer by it, has been grafted with slow
The minor comonomer of effect is released, obtained polymerizate molecular structure is controllable, narrow molecular weight distribution, is ensureing concrete initial fluidity
Meanwhile the mobility slow-release capability more more excellent than conventional free radical polymerizate is shown, and the reactions steps are simple, peace
Loopful is protected, and repeatability is strong.
The invention provides a kind of method that sustained-release polycarboxylic water reducer is prepared based on ATRP, leads to
Cross after ATRP first prepares polymeric monomer initiator and prepare sustained-release polycarboxylic water reducer material, including following bar
Part and step：
(1) prepared by polymeric monomer initiator：It is filled with nitrogen in the reactor first 3-5 times, continues inflated with nitrogen after excluding oxygen
Reactor is kept nitrogen atmosphere, sequentially add unsaturated acyl amine minor comonomer, organic solvent, part, transition metal afterwards
Mixture catalyst, halogenated compound initiator, and 5-20 minutes are stirred during feeding every time, it is warming up at 50-90 DEG C and carries out
Atom transition free radical polymerization reaction, 2-8 hours are reacted, obtain polymeric monomer initiator；
(2) prepared by sustained-release polycarboxylic water reducer：Salt unsaturated carboxylic acid, esters of unsaturated carboxylic acids are sequentially added into reactor
Class minor comonomer, unsaturated polyether polymeric monomer, repeatedly persistently filled after the Frozen-thawed cycled of 3-5 freezing-inflated with nitrogen-defrosting afterwards
Nitrogen keeps nitrogen atmosphere, and it is big single to sequentially add gained in organic solvent, part, transition metal compound catalyst, step (1)
Body initiator, and feeding interval mixing time 5-20 minutes every time, it is warming up to progress atom transferred free radical at 50-90 DEG C and gathers
Reaction is closed, 5-8 hours is reacted, is eventually adding Organic Alcohol, repeatedly washing precipitation 3-5 times, vacuum is done at 40-80 DEG C by sediment
It is dry to constant weight, add aqueous solvent obtain needed for concentration sustained-release polycarboxylic water reducer solution；
Wherein, the unsaturated acyl amine minor comonomer described in step (1) is acrylamide, methacrylic, N- isopropyls
Butylmethacrylamide or NIPA；Organic solvent described in step (1) is toluene, dimethylbenzene, acetone, ring
Described in hexanone, dioxane, dimethylformamide, methyl phenyl ethers anisole, tetrahydrofuran or dimethyl sulfoxide (DMSO), dosage and step (1)
The mass ratio of unsaturated acyl amine minor comonomer is 1-2:1；Part described in step (1) is 2,2- bipyridyls, pentamethyl two is sub-
Ethyl triamine, tetramethylethylenediamine, hexamethyl trien or four-(2- pyridylmethyls) ethylenediamine, dosage and steps
(1) mol ratio of the unsaturated acyl amine minor comonomer described in is 0.01-0.05:1；Transition metal described in step (1)
Mixture catalyst includes cuprous bromide, stannous chloride, ferrous bromide or frerrous chloride, dosage and the insatiable hunger described in step (1)
Mol ratio with amide-type minor comonomer is 0.01-0.05:1；Halogenated compound initiator described in step (1) is 2- isobutyl bromides
Ethyl ester, 2 bromopropionic acid methyl esters, 2- chlorine propionamide, 2- bromines propionamide, 2- bromine isobutyl acylbromides, 2- chlorpromazine chlorides or 2- bromo propionyl chloros,
Dosage and the mol ratio of the unsaturated acyl amine minor comonomer described in step (1) are 0.01-0.03:1；
Unsaturated polyether polymeric monomer described in step (2) is allyl polyethenoxy ether, methyl alkenyl APEO,
Isopentene group APEO or isobutenyl APEO；Salt unsaturated carboxylic acid described in step (2) is PAA,
Sodium methacrylate, potassium acrylate or methacrylic acid potassium, dosage are rubbed with the unsaturated polyether polymeric monomer described in step (2)
Your ratio is 1-5:1；Unsaturated carboxylate type minor comonomer described in step (2) is methyl acrylate, methyl methacrylate, third
Olefin(e) acid ethyl ester, EMA, n-butyl acrylate, n-BMA, isobutyl acrylate, methacrylic acid
Isobutyl ester, tert-butyl acrylate, Tert-butyl Methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate, ten
Dialkacrylates, dodecyl methyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, metering system
Sour isobornyl thiocyanoacetate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylic acid
Stearyl or octadecyl methacrylate, dosage and mole of the unsaturated polyether polymeric monomer described in step (2)
Than for 1-5:1；Salt unsaturated carboxylic acid and unsaturated carboxylate type minor comonomer, three kinds of unsaturated polyether polymeric monomer in step (2)
Monomer summation and the mol ratio of polymeric monomer initiator obtained by step (1) are 1-7：1；Organic solvent described in step (2) is first
Benzene, dimethylbenzene, acetone, cyclohexanone, dioxane, dimethylformamide, methyl phenyl ethers anisole, tetrahydrofuran or dimethyl sulfoxide (DMSO), dosage
Mass ratio with the unsaturated polyether polymeric monomer described in step (2) is 2-5:1；Part described in step (2) joins for 2,2-
Pyridine, five methyl diethylentriamine, tetramethylethylenediamine, hexamethyl trien or four-(2- pyridylmethyls) second
Diamines, dosage and the mol ratio of the unsaturated polyether polymeric monomer described in step (1) are 0.01-0.05:1；Described in step (2)
Transition metal compound catalyst include cuprous bromide, stannous chloride, ferrous bromide or frerrous chloride, dosage and step (1)
Described in the mol ratio of unsaturated polyether polymeric monomer be 0.01-0.05:1；Organic Alcohol described in step (2) is methanol, second
Alcohol, isopropanol, dosage and the mass ratio of the unsaturated polyether polymeric monomer described in step (2) are 8-20:1；Described in step (2)
Water and step (2) described in unsaturated polyether polymeric monomer mass ratio 4-6:1.
Unsaturated ether polymeric monomer molecular weight is 500-3000 in the inventive method.
The inventive method has the advantages that compared with prior art：
1. the present invention prepares initiator, disposably to unsaturated ethers according to design theory of molecular structure with amide-type monomer
Class polymeric monomer, unsaturated carboxylic acid salt minor comonomer and unsaturated carboxylate type minor comonomer carry out ATRP, this
It is the breakthrough application to the type polymerization methodses, and the structural innovation to sustained-release polycarboxylic water reducer.The invention is not
The application performance of polycarboxylate water-reducer is only improved, and new think of is provided for research polycarboxylic acid structure and the relation of its performance
Road, the developing direction of polycarboxylate water-reducer is widened.
2. relative to common poly carboxylic acid series water reducer, sustained-release polycarboxylic water reducer prepared by the present invention contains acid amides knot
Structure, the aqueous solution is pointed to, constitutes unimolecule or polymolecular in cement particle surface, hydrophilic radical by providing anchoring group absorption
Adsorbed film, electrostatic repulsion is produced while reducing surface tension.In addition, the introducing of amide structure can be with hydrone and polyethers side
Interchain forms firm hydrogen bond action, therefore also acts the effect for strengthening steric hindrance.Incorporation contains amide structure water reducer
Complexing can also be produced by the calcium ion in its nitrogen-atoms and cement, significantly postpones heat evolution velocity and reduces peak position heat
Value.Because the hydrogen of amide structure is easily dissociated into proton, preferable interaction can be formed with the cement system of alkalescence, be advantageous to subtract
Relative lubrication wetting of the aqua aqueous solution cement surface, infiltration, absorption and particles of aggregates.
3. the present invention is prepared using Transfer Radical Polymerization, it is characterized in that reaction can rely on catalyst and part
Input amount controls, and adjustable molecular weight section, so as to obtain preferable polycarboxylic acids backbone length, is advantageous to polycarboxylate water-reducer in coagulation
Dispersiveness and stability in soil.The polymerisation narrow molecular weight distribution, the single purity of product is high, also may be used under low-dosage
Reach and effect same under conventional water reducing agents high additive.This method is advantageous to Molecular Design, and a large amount of eluting groups are existed
Polycarboxylic acids main chain is introduced during design synthesis so that its mobility to concrete has slow release effect, so as to effectively prevent
Concrete mix water loss and evaporation caused by transporting with high temperature, while avoid may be because of the excessive appearance of the slump
Excreting water phenomenon, make concrete that there is preferable mobility holding capacity.
4. the inventive method is to prepare sustained-release polycarboxylic water reducer using ATRP, it is sustained with tradition
Type water reducer is compared, and whole process is simple and easy to control, does not have particular/special requirement to experimental facilities, and the polymerization used can grasped commonly
Completed under the conditions of work, and there is more excellent mobility and holding capacity than traditional polycarboxylate water-reducer, be the poly- carboxylic of spacetabs type
The preparation of sour water reducer provides new method, and can degree of design height, the controllable, narrow molecular weight distribution of molecular weight etc. with molecule
Advantage, there is good promotional value and application prospect.
5. the sustained-release polycarboxylic water reducer that the present invention synthesizes shows excellent flowing retention property, be on the one hand its more
Cement particle surface easily is adsorbed in, its mobility can reach application with flowing holding capacity under relatively lower volume
Standard, on the other hand it is that it can significantly improve the dispersion and dispersion stability of cement granules, the cement of different cultivars is shown
Good adaptability.In addition, the polycarboxylate water-reducer Product Status is stable, under high concentration state will not static layering, also not
Understand crystalline metamorphism at low temperature.The synthetic method step is simple and convenient, nontoxic, environment friendly and pollution-free, is advantageous to industrialization and pushes away
Extensively with application, there is good economic benefit and social benefit.
Embodiment
The present invention is described in further detail with reference to embodiment, but the implementation not limited to this of the present invention.
Embodiment 1
It is filled with nitrogen in the reactor first 3 times, continuation inflated with nitrogen makes reactor keep nitrogen atmosphere after excluding oxygen, it
After sequentially add 7.1g acrylamides, 7.1g toluene, the arsenic pyridine of 0.16g 2,2- connection, 0.14g cuprous bromides, 0.2g 2 bromopropionic acids
Ethyl ester, and stirred 5 minutes during feeding every time, it is warming up at 90 DEG C and carries out atom transition free radical polymerization reaction, reaction 5 is small
When, obtain polymeric monomer initiator；9.4g PAAs, 17.2g methyl acrylates, 50g pi-allyls are sequentially added into reactor
APEO (molecular weight=500), after being repeated 3 times the Frozen-thawed cycled of freezing-inflated with nitrogen-defrosting afterwards, continue inflated with nitrogen
Nitrogen atmosphere is kept, sequentially adds 100g toluene, the pyridine of 0.16g 2,2- connection arsenic, before 0.14g cuprous bromides, gained polymeric monomer
Initiator, and stirred 5 minutes during feeding every time, it is warming up at 50 DEG C and carries out atom transition free radical polymerization reaction, reaction 8
Hour, 550g methanol is eventually adding, repeatedly washing precipitation 5 times, sediment is dried under vacuum to constant weight at 80 DEG C, adds 200g
Aqueous solvent obtains the polycarboxylate water-reducer solution that mass fraction is 40%；
Embodiment 2
After the polycarboxylate water-reducer that the concentration that embodiment 1 is obtained is 40% is deposited 30 days at 7 DEG C, determine it and implement effect
Fruit.
Embodiment 3
It is filled with nitrogen in the reactor first 5 times, continuation inflated with nitrogen makes reactor keep nitrogen atmosphere after excluding oxygen, it
After sequentially add 12.7g N- isopropyl acrylamides, 12.7g acetone, 0.248g tetramethylethylenediamines, 0.645g brominations
Ferrous, 0.15g 2- bromine propionamides, and stirred 15 minutes during feeding every time, it is warming up at 70 DEG C and carries out atom transfer freedom
Base polymerisation, react 7 hours, obtain polymeric monomer initiator；16.5g potassium acrylates, 20g propylene are sequentially added into reactor
Acetoacetic ester, 100g methyl alkenyl APEOs (molecular weight=1000), the jelly of freezing-inflated with nitrogen-defrosting is repeated 5 times afterwards
After melting circulation, continue inflated with nitrogen and keep nitrogen atmosphere, sequentially add 200g acetone, 0.017g tetramethylethylenediamines, 0.032g
Ferrous bromide, before gained polymeric monomer initiator, and stirred 15 minutes during feeding every time, it is warming up at 50 DEG C and carries out atom
Transition free radical polymerization reaction, react 8 hours, be eventually adding 1000g isopropanols, repeatedly washing precipitation 3 times, by sediment 60
Constant weight is dried under vacuum at DEG C, 320g aqueous solvents is added and obtains the polycarboxylate water-reducer solution that mass fraction is 50%；
Embodiment 4
After the polycarboxylate water-reducer that the concentration that embodiment 5 is obtained is 50% is deposited 20 days at 6 DEG C, determine it and implement effect
Fruit.
Embodiment 5
It is filled with nitrogen in the reactor first 4 times, continuation inflated with nitrogen makes reactor keep nitrogen atmosphere after excluding oxygen, it
After sequentially add 7.1g acrylamides, 7.1g dioxane, 2.12g tetra--(2- pyridylmethyls) ethylenediamine, 0.72g protobromides
Copper, 0.458g 2- bromine isobutyl acylbromides, and stirred 5 minutes during feeding every time, it is warming up at 70 DEG C and carries out atom transfer freedom
Base polymerisation, react 7 hours, obtain polymeric monomer initiator；9.4g PAAs, 25.63g third are sequentially added into reactor
Olefin(e) acid N-butyl, 50g isopentene groups APEO (molecular weight=500), are repeated 4 times freezing-inflated with nitrogen-defrosting afterwards
After Frozen-thawed cycled, continue inflated with nitrogen and keep nitrogen atmosphere, sequentially add 150g dioxane, 2.12g tetra--(2- pyridine radicals first
Base) ethylenediamine, 0.72g cuprous bromides, before gained polymeric monomer initiator, and every time feed during stir 5 minutes, be warming up to
Atom transition free radical polymerization reaction is carried out at 70 DEG C, reacts 6 hours, is eventually adding 500g ethanol, repeatedly washing precipitation 3 times,
Sediment is dried under vacuum to constant weight at 80 DEG C, 265g aqueous solvents is added and obtains the polycarboxylate water-reducer that mass fraction is 45%
Solution；
Embodiment 6
After the polycarboxylate water-reducer that the concentration that embodiment 9 is obtained is 45% is deposited 40 days at 9 DEG C, determine it and implement effect
Fruit.
Embodiment 7
It is filled with nitrogen in the reactor first 3 times, continuation inflated with nitrogen makes reactor keep nitrogen atmosphere after excluding oxygen, it
After sequentially add 11.31g NIPAs, 22.62g cyclohexanone, 0.92g hexamethyls trien, 0.5g chlorine
Change ferrous, 0.214g 2- chlorine propionamides, and stirred 20 minutes during feeding every time, be warming up at 60 DEG C and carry out atom transfer
Raolical polymerizable, react 8 hours, obtain polymeric monomer initiator；24.8g methacrylic acids are sequentially added into reactor
Potassium, 28.53g EMAs, 150g isobutenyls APEO (molecular weight=3000), are repeated 3 times cold afterwards
After the Frozen-thawed cycled of jelly-inflated with nitrogen-defrosting, continue inflated with nitrogen keep nitrogen atmosphere, sequentially add 300g cyclohexanone,
0.46g hexamethyls trien, before 0.25g frerrous chlorides, gained polymeric monomer initiator, and stirred during feeding every time
Mix 20 minutes, be warming up at 60 DEG C and carry out atom transition free radical polymerization reaction, react 7 hours, be eventually adding 1500g methanol,
Washing precipitation 5 times repeatedly, sediment is dried under vacuum to constant weight at 70 DEG C, addition 625g aqueous solvents obtain mass fraction and are
40% polycarboxylate water-reducer solution；
Embodiment 8
After the polycarboxylate water-reducer that the concentration that embodiment 7 is obtained is 40% is deposited 30 days at 8 DEG C, determine it and implement effect
Fruit.
Embodiment 9
It is filled with nitrogen in the reactor first 4 times, continuation inflated with nitrogen makes reactor keep nitrogen atmosphere after excluding oxygen, it
After sequentially add 8.51g Methacrylamides, 17.02g dimethylbenzene, 0.25g five methyl diethylentriamines, 0.2g protochlorides
Copper, 0.23g 2 bromopropionic acid methyl esters, and stirred 10 minutes during feeding every time, it is warming up at 80 DEG C and carries out atom transfer freedom
Base polymerisation, react 6 hours, obtain polymeric monomer initiator；10.8g Sodium methacrylates, 15g are sequentially added into reactor
Methyl methacrylate, 50g allyl polyethenoxy ethers (molecular weight=1000), are repeated 4 times freezing-inflated with nitrogen-solution afterwards
After the Frozen-thawed cycled of jelly, continue inflated with nitrogen and keep nitrogen atmosphere, sequentially add 150g dimethylbenzene, two sub- second of 0.12g pentamethyls
Base triamine, before 0.1g stannous chlorides, gained polymeric monomer initiator, and stirred 10 minutes during feeding every time, it is warming up to 60
Atom transition free radical polymerization reaction is carried out at DEG C, reacts 7 hours, is eventually adding 700g ethanol, repeatedly washing precipitation 4 times, will
Sediment is dried under vacuum to constant weight at 70 DEG C, and it is molten that addition 375g aqueous solvents obtain the polycarboxylate water-reducer that mass fraction is 20%
Liquid；
Embodiment 10
After the polycarboxylate water-reducer that the concentration that embodiment 3 is obtained is 20% is deposited 20 days at 7 DEG C, determine it and implement effect
Fruit.
Embodiment 11
It is filled with nitrogen in the reactor first 5 times, continuation inflated with nitrogen makes reactor keep nitrogen atmosphere after excluding oxygen, it
After sequentially add 8.51g Methacrylamides, 17.02g dimethylformamides, 0.16g 2,2- bipyridyls, 0.1g stannous chlorides,
0.38g 2- chlorpromazine chlorides, and stirred 10 minutes during feeding every time, it is warming up to progress atom transferred free radical at 80 DEG C and gathers
Reaction is closed, reacts 6 hours, obtains polymeric monomer initiator；10.8g Sodium methacrylates, 42.6g first are sequentially added into reactor
Base tert-butyl acrylate, 100g methyl alkenyl APEOs (molecular weight=1000), be repeated 5 times afterwards freezing-inflated with nitrogen-
After the Frozen-thawed cycled of defrosting, continue inflated with nitrogen and keep nitrogen atmosphere, sequentially add 200g dimethylformamides, 0.16g 2,2-
Bipyridyl, before 0.1g stannous chlorides, gained polymeric monomer initiator, and stirred 10 minutes during feeding every time, it is warming up to 90
Atom transition free radical polymerization reaction is carried out at DEG C, reacts 5 hours, is eventually adding 1000g isopropanols, repeatedly washing precipitation 5 times,
Sediment is dried under vacuum to constant weight at 70 DEG C, 673.1g aqueous solvents is added and obtains the polycarboxylic acids diminishing that mass fraction is 30%
Agent solution；
Embodiment 12
After the polycarboxylate water-reducer that the concentration that embodiment 10 is obtained is 30% is deposited 40 days at 9 DEG C, its implementation is determined
Effect.
Implementation result：
1. flowing degree of net paste of cement
The characteristics of this product maximum is compared to other polycarboxylate water-reducers in the identical ratio of mud, to the mobility of concrete
With slow release effect, experiment determines under identical volume each embodiment to the paste flowing degree of different cement types.Experiment is pressed
GB/T8077-2012《Methods for testing uniformity of concrete admixture》Carry out, W/C=0.29, volume is the solid volume of folding.From existing
Commercially available slow-release type polycarboxylate water reducer (comparative example) is as a comparison sample.Result of the test is shown in Table 1.
The pulp flowage results of property of table 1
From table 1 it follows that the sustained-release polycarboxylic water reducer solution of the inventive method synthesis, in 0.29 ratio of mud
Under the 0.20% solid volume of folding, excellent dispersion holding capacity and cement adaptability can be shown.
2. low-dosage paste flowing degree
This product is in the case of low-dosage (0.12-0.18), with other polycarboxylate water-reducers in the identical ratio of mud, cement
Net slurry can still keep higher dispersive property.GB/T8077-2012 is pressed in experiment《Methods for testing uniformity of concrete admixture》Enter
OK, cement selection reference cement, W/C=0.29.From existing commercially available sustained-release polycarboxylic water reducer (comparative example) conduct pair
Compare sample.Result of the test is shown in Table 2.
Pulp flowage results of property under the low-dosage of table 2
From Table 2, it can be seen that the sustained-release polycarboxylic water reducer solution of the inventive method synthesis has under low-dosage
There is preferably net slurry mobility holding capacity, and it is more excellent than control sample effect.
3. concrete slump and divergence
As a comparison sample from existing commercially available sustained-release polycarboxylic water reducer (comparative example), experiment determines each implementation
The divergence and the slump and retention property that example is shown in concrete system.Result of the test is shown in Table 3.
The concrete flowability energy result of table 3
From table 3 it is observed that the sustained-release polycarboxylic water reducer solution of the inventive method synthesis is in concrete system
The holding capacity of excellent divergence and the slump can be shown.
Claims (2)
- A kind of 1. method that sustained-release polycarboxylic water reducer is prepared based on ATRP, it is characterised in that pass through ATRP first prepares the condition and step that sustained-release polycarboxylic water reducer material is prepared after polymeric monomer initiator It is as follows：(1) prepared by polymeric monomer initiator：It is filled with nitrogen in the reactor first 3-5 times, continuation inflated with nitrogen makes instead after excluding oxygen Answer device to keep nitrogen atmosphere, sequentially add unsaturated acyl amine minor comonomer, organic solvent, part, transistion metal compound afterwards Catalyst, halogenated compound initiator, and 5-20 minutes are stirred during feeding every time, it is warming up at 50-90 DEG C and carries out atom Transition free radical polymerization reaction, 2-8 hours are reacted, obtain polymeric monomer initiator；(2) prepared by sustained-release polycarboxylic water reducer：It is small that salt unsaturated carboxylic acid, unsaturated carboxylate type are sequentially added into reactor Monomer, unsaturated polyether polymeric monomer, afterwards repeatedly after the Frozen-thawed cycled of 3-5 freezing-inflated with nitrogen-defrosting, continue inflated with nitrogen Nitrogen atmosphere is kept, gained polymeric monomer in organic solvent, part, transition metal compound catalyst, step (1) is sequentially added and draws Agent, and feeding interval mixing time 5-20 minutes every time are sent out, it is anti-to be warming up to progress ATRP at 50-90 DEG C Should, 5-8 hours are reacted, are eventually adding Organic Alcohol, washing precipitation 3-5 times, sediment is dried under vacuum at 40-80 DEG C repeatedly Constant weight, add aqueous solvent and obtain sustained-release polycarboxylic water reducer solution；Wherein, the unsaturated acyl amine minor comonomer described in step (1) is acrylamide, methacrylic, N- isopropyl first Base acrylamide or NIPA；Organic solvent described in step (1) is toluene, dimethylbenzene, acetone, hexamethylene Described in ketone, dioxane, dimethylformamide, methyl phenyl ethers anisole, tetrahydrofuran or dimethyl sulfoxide (DMSO), dosage and step (1) not The mass ratio of saturated amide class minor comonomer is 1-2:1；Part described in step (1) is 2,2- bipyridyls, two sub- second of pentamethyl Base triamine, tetramethylethylenediamine, hexamethyl trien or four-(2- pyridylmethyls) ethylenediamines, dosage and step (1) Described in the mol ratio of unsaturated acyl amine minor comonomer be 0.01-0.05:1；Transistion metal compound described in step (1) Catalyst includes cuprous bromide, stannous chloride, ferrous bromide or frerrous chloride, dosage and the unsaturated acyl described in step (1) The mol ratio of amine minor comonomer is 0.01-0.05:1；Halogenated compound initiator described in step (1) is 2- isobutyl bromide second Ester, 2 bromopropionic acid methyl esters, 2- chlorine propionamide, 2- bromines propionamide, 2- bromine isobutyl acylbromides, 2- chlorpromazine chlorides or 2- bromo propionyl chloros, use Amount and the mol ratio of the unsaturated acyl amine minor comonomer described in step (1) are 0.01-0.03:1；Unsaturated polyether polymeric monomer described in step (2) is allyl polyethenoxy ether, methyl alkenyl APEO, isoamyl Alkenyl APEO or isobutenyl APEO；Salt unsaturated carboxylic acid described in step (2) is PAA, methyl PAA, potassium acrylate or methacrylic acid potassium, dosage and the mol ratio of the unsaturated polyether polymeric monomer described in step (2) For 1-5:1；Unsaturated carboxylate type minor comonomer described in step (2) is methyl acrylate, methyl methacrylate, acrylic acid Ethyl ester, EMA, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl Ester, tert-butyl acrylate, Tert-butyl Methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate, dodecane Base acrylate, dodecyl methyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, methacrylic acid are different Norbornene ester, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylic acid 18 Arrcostab or octadecyl methacrylate, dosage and the mol ratio of the unsaturated polyether polymeric monomer described in step (2) are 1-5:1；Organic solvent described in step (2) is toluene, dimethylbenzene, acetone, cyclohexanone, dioxane, dimethylformamide, Methyl phenyl ethers anisole, tetrahydrofuran or dimethyl sulfoxide (DMSO), dosage and the mass ratio of the unsaturated polyether polymeric monomer described in step (2) are 2- 5:1；Part described in step (2) is 2,2- bipyridyls, five methyl diethylentriamine, tetramethylethylenediamine, hexamethyl three Ethylene tetra or four-(2- pyridylmethyls) ethylenediamines, dosage are rubbed with the unsaturated polyether polymeric monomer described in step (2) Your ratio is 0.01-0.05:1；Transition metal compound catalyst described in step (2) is cuprous bromide, stannous chloride, bromination Ferrous or frerrous chloride, dosage and the mol ratio of the unsaturated polyether polymeric monomer described in step (2) are 0.01-0.05:1；Step Suddenly the Organic Alcohol described in (2) is methanol, ethanol, isopropanol, the unsaturated polyether polymeric monomer described in dosage and step (2) Mass ratio is 8-20:1；Aqueous solvent and the mass ratio of the unsaturated polyether polymeric monomer described in step (2) described in step (2) 4-6:1。
- 2. the preparation method of sustained-release polycarboxylic water reducer according to claim 1, it is characterised in that step (2) is described Salt unsaturated carboxylic acid, three kinds of monomer summations of unsaturated carboxylate type minor comonomer and unsaturated polyether polymeric monomer and step (1) The mol ratio of the polymeric monomer initiator of middle gained is 1-7：1.
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